Fiber-reinforced resin composition and molded body thereof

ABSTRACT

Long-fiber-reinforced thermoplastic resin particles and a blend thereof are provided, wherein the opening property of the reinforcing fibers during molding is good, and a molded body exhibiting an excellent appearance and having high mechanical strength is obtained. The particles (A) contains a thermoplastic resin (A1), produced by using a metallocene catalyst, a modified polyolefin resin (A2) modified with an unsaturated carboxylic acid or a derivative thereof, and reinforcing fibers (A3) and satisfy the following requirements (1) to (5); (1) the amount of modification of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 2 percent by weight in 100 percent by weight of the total of (A1) and (A2); (2) (A1) and (A2) constitute 20 to 70 percent by weight in 100 percent by weight of the total of (A1), (A2), and (A3); (3) (A3) constitutes 30 to 80 percent by weight in 100 percent by weight of the total of (A1), (A2), and (A3); (4) when 25 g of (A) is encapsulated in a 20-L chamber and is stood at 65° C. for 1 hour, the amount of acetaldehyde dissipated from (A) is 3.0 μg/m 3  or less; and (5) the melting point of the resin component in (A) is 150° C. or higher.

TECHNICAL FIELD

The present invention relates to a fiber-reinforced resin compositionand a molded body thereof. In particular, the present invention relatesto long-fiber-reinforced thermoplastic resin particles, along-fiber-reinforced thermoplastic resin particle blend, and a moldedbody thereof.

BACKGROUND ART

Many molded bodies formed from long-fiber-reinforced resin compositionshave been used as automobile module parts required to have highstrength. However, in some cases, reinforcing fibers appear in lumps ona module part surface due to poor dispersion of reinforcing fiberscontained in the long-fiber-reinforced resin composition. Consequently,it is necessary that the module part formed from thelong-fiber-reinforced resin composition is used as a part of a portionwhere a required level of appearance is low or is used after painting isapplied to the surface thereof.

In order to solve the above-described problems, a fiber-reinforced resincomposition has been reported, wherein an appearance of the resultingmolded body has been improved (refer to PTLs 1 to 4).

For example, PTLs 3 and 4 report long-fiber-reinforced resincompositions produced by melt-kneading a combination of a propylenepolymer having a narrow molecular weight distribution and a propylenepolymer having a wide molecular weight distribution together withreinforcing fibers, as well as pellets and a molded body formed from thecomposition. However, an improvement in dispersibility of thereinforcing fibers contained in the long-fiber-reinforced resincomposition and a high level of appearance required of an automobilemodule part produced through injection molding are not completelysatisfied. Consequently, further improvement in appearance has beenrequired.

CITATION LIST Patent Literature

-   PTL 1: Japanese Unexamined Patent Application Publication No.    2004-300293-   PTL 2: Japanese Unexamined Patent Application Publication No.    2006-193735-   PTL 3: Japanese Unexamined Patent Application Publication No.    2008-179784-   PTL 4: Japanese Unexamined Patent Application Publication No.    2008-179785

SUMMARY OF INVENTION Technical Problem

It is an object of the present invention to providelong-fiber-reinforced thermoplastic resin particles and along-fiber-reinforced thermoplastic resin particle blend, wherein theopening property of the reinforcing fibers during molding is good, and amolded body exhibiting an excellent appearance and having highmechanical strength, e.g., bending strength, is obtained.

Solution to Problem

The present inventors conducted intensive research. As a result, it wasfound that long-fiber-reinforced thermoplastic resin particlescontaining a thermoplastic resin produced by using a metallocenecatalyst, a modified polyolefin resin, and reinforcing fibers, or along-fiber-reinforced thermoplastic resin particle blend formed from thelong-fiber-reinforced thermoplastic resin particles and polyolefin resinparticles for dilution exhibited a good opening property of thereinforcing fibers during molding and was able to provide a molded bodyexhibiting an excellent appearance and having excellent mechanicalstrength. Consequently, the present invention has been completed.

That is, the present invention includes the following items.

[1] Long-fiber-reinforced thermoplastic resin particles (A)characterized by including a thermoplastic resin (A1) produced by usinga metallocene catalyst, a modified polyolefin resin (A2) modified withan unsaturated carboxylic acid or a derivative thereof, and reinforcingfibers (A3), wherein the following requirements (1) to (5) aresatisfied.

(1) The amount of modification of the unsaturated carboxylic acid or aderivative thereof is 0.01 to 2 percent by weight in 100 percent byweight of the total of the thermoplastic resin (A1) and the modifiedpolyolefin resin (A2).(2) The total of the thermoplastic resin (A1) and the modifiedpolyolefin resin (A2) constitute 20 to 70 percent by weight in 100percent by weight of the total of the thermoplastic resin (A1), themodified polyolefin resin (A2), and the reinforcing fibers (A3).(3) The reinforcing fibers (A3) constitute 30 to 80 percent by weight in100 percent by weight of the total of the thermoplastic resin (A1), themodified polyolefin resin (A2), and the reinforcing fibers (A3).(4) When 25 g of the long-fiber-reinforced thermoplastic resin particles(A) are encapsulated in a 20-L chamber and are stood at 65° C. for 1hour, the amount of acetaldehyde dissipated from thelong-fiber-reinforced thermoplastic resin particles (A) is 3.0 μg/m³ orless.(5) The melting point of the resin component in thelong-fiber-reinforced thermoplastic resin particles (A) is 150° C. orhigher.

[2] The long-fiber-reinforced thermoplastic resin particles (A)according to the item [1], characterized in that the thermoplastic resin(A1) constitutes 75 to 99 percent by weight and the modified polyolefinresin (A2) constitutes 1 to 25 percent by weight in 100 percent byweight of the total of the above-described thermoplastic resin (A1) andthe above-described modified polyolefin resin (A2).

[3] The long-fiber-reinforced thermoplastic resin particles (A)according to the item [1] or item [2], characterized in that theabove-described thermoplastic resin (A1) satisfies the followingrequirements (a-1), (a-2), and (a-3).

(a-1) The melt index (MI; resin temperature 230° C., load 21.18 N) iswithin the range of 100 to 250 g/10 min.(a-2) The amount of components soluble into o-dichlorobenzene at 90° C.measured by cross fractionation chromatography (CFC method) is 1 percentby weight or less.(a-3) The molecular weight distribution (Mw/Mn) is less than 3.5.

[4] The long-fiber-reinforced thermoplastic resin particles (A)according to any one of the items [1] to [3], characterized in that theabove-described thermoplastic resin (A1) is at least one type of polymerselected from propylene homopolymers and propylene-α-olefin randomcopolymers.

[5] A long-fiber-reinforced thermoplastic resin particle blend (C)characterized by including 10 to 90 percent by weight oflong-fiber-reinforced thermoplastic resin particles (A) according to anyone of the items [1] to [4], and 90 to 10 percent by weight ofpolyolefin resin particles (B) for dilution (where the total of thelong-fiber-reinforced thermoplastic resin particles (A) and thepolyolefin resin particles (B) for dilution is assumed to be 100 percentby weight).

[6] The long-fiber-reinforced thermoplastic resin particle blend (C)according to the item [5], characterized in that the reinforcing fibers(A3) constitute 5 to 60 percent by weight in 100 percent by weight ofthe total of the above-described long-fiber-reinforced thermoplasticresin particles (A) and the above-described polyolefin resin particles(B) for dilution.

[7] The long-fiber-reinforced thermoplastic resin particle blend (C)according to the item [5] or item [6], characterized in that theabove-described polyolefin resin particles (B) for dilution satisfy thefollowing requirements (b-1), (b-2), and (b-3).

(b-1) The melt index (MI; resin temperature 230° C., load 21.18 N) iswithin the range of 20 to 70 g/10 min.(b-2) The relaxation time λ is 0.3 seconds or shorter, where the angularfrequency ω=1 (rad/sec), which is calculated from the storage modulus G′and the loss modulus G″ measured with a cone & plate rheometer.(b-3) The molecular weight distribution (Mw/Mn) is within the range of2.5 to 6.0.

[8] A molded body produced through molding by usinglong-fiber-reinforced thermoplastic resin particles (A) according to anyone of the items [1] to [4].

[9] A molded body produced through molding by usinglong-fiber-reinforced thermoplastic resin particle blend (C) accordingto any one of the items [5] to [7].

Advantageous Effects of Invention

According to the present invention, the long-fiber-reinforcedthermoplastic resin particles and the long-fiber-reinforcedthermoplastic resin particle blend, from which a molded body exhibitingan excellent appearance and having high mechanical strength is obtained,can be provided.

According to the present invention, the long-fiber-reinforcedthermoplastic resin particle dry blend formed from thelong-fiber-reinforced thermoplastic resin particles containing athermoplastic resin having high fluidity and the polyolefin resinparticles for dilution having low fluidity is used and, thereby, aninjection-molded body is obtained, wherein the opening property of thereinforcing fibers in an injection cylinder is good and raising of fiberlumps on the molded body surface is suppressed during injection molding.

Furthermore, the molded body according to the present invention is usedfor automobile parts favorably because a volatile organic compound (VOC)is not generated.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram of a pellet manufacturing apparatus.

FIG. 2 is a diagram showing a plot of the results, where a vibrationtest was performed at 23° C. in the MD direction.

FIG. 3 is a diagram showing a plot of the results, where a vibrationtest was performed at 23° C. in the TD direction.

FIG. 4 is a diagram showing a plot of the results, where a vibrationtest was performed at 90° C. in the MD direction.

FIG. 5 is a diagram showing a plot of the results, where a vibrationtest was performed at 90° C. in the TD direction.

DESCRIPTION OF EMBODIMENTS

Long-fiber-reinforced thermoplastic resin particles (A), along-fiber-reinforced thermoplastic resin particle blend (C) (hereaftermay be simply referred to as a “resin blend (C)”), and a molded bodythereof according to the present invention will be described below indetail.

[Long-Fiber-Reinforced Thermoplastic Resin Particles (A)]

Long-fiber-reinforced thermoplastic resin particles (A) according to thepresent invention are characterized by including a thermoplastic resin(A1) produced by using a metallocene catalyst, a modified polyolefinresin (A2) modified with an unsaturated carboxylic acid or a derivativethereof, and reinforcing fibers (A3), wherein the following requirements(1) to (5) are satisfied.

(1) The amount of modification of the unsaturated carboxylic acid or aderivative thereof is 0.01 to 2 percent by weight in 100 percent byweight of the total of the thermoplastic resin (A1) and the modifiedpolyolefin resin (A2).(2) The thermoplastic resin (A1) and the modified polyolefin resin (A2)constitute 20 to 70 percent by weight in 100 percent by weight of thetotal of the thermoplastic resin (A1), the modified polyolefin resin(A2), and the reinforcing fibers (A3).(3) The reinforcing fibers (A3) constitute 30 to 80 percent by weight in100 percent by weight of the total of the thermoplastic resin (A1), themodified polyolefin resin (A2), and the reinforcing fibers (A3).(4) When 25 g of the long-fiber-reinforced thermoplastic resin particles(A) are encapsulated in a 20-L chamber and are stood at 65° C. for 1hour, the amount of acetaldehyde dissipated from thelong-fiber-reinforced thermoplastic resin particles (A) is 3.0 μg/m³ orless.(5) The melting point of the resin component in thelong-fiber-reinforced thermoplastic resin particles (A) is 150° C. orhigher.

<Thermoplastic Resin (A1)>

As for the thermoplastic resin (A1) according to the present invention,for example, polyolefin based resins, polystyrene based resins, and thelike can be used. Specific examples of polyolefin based resins includepolypropylene based resins, e.g., propylene homopolymers andpropylene-α-olefin random copolymers, and 4-methyl-1-pentene polymerresin. Here, specific examples of α-olefins include ethylene, 1-butene,1-pentene, 1-hexene, and 1-octene. Particularly preferable examplesinclude ethylene and 1-butene. One type of α-olefin may be used alone,or at least two types may be used in combination. Among them,polypropylene based resins are preferable, and in particular, propylenehomopolymers are preferable from the viewpoint of the moldability andthe heat resistance. Specific examples of polystyrene based resinsinclude syndiotactic polystyrenes.

As for a method for manufacturing the thermoplastic resin (A1), apublicly known manufacturing method is used, in which a metallocenecatalyst containing a metallocene compound including a ligand having acyclopentadienyl skeleton in the molecule is employed. For example,manufacturing methods described in International Publication No.01/27124, Japanese Unexamined Patent Application Publication No.11-315109, and the like can be employed. Examples of metallocenecompounds include two types, that is, metallocene compounds representedby the following general formula [I] and cross-linked metallocenecompounds represented by the following general formula [II], from theviewpoint of the chemical structure. Among them, the cross-linkedmetallocene compounds are preferable.

In the above-described general formulae [I] and [II], M represents atitanium atom, a zirconium atom, or a hafnium atom, Q represents ahalogen atom, a hydrocarbon group, or a group selected from an anionicligand and a neutral ligand capable of coordinating with a lone electronpair, j represents an integer of 1 to 4, and Cp¹ and Cp² represent acyclopentadienyl group or a substituted cyclopentadienyl group, whereCp¹ and Cp² may be the same or different and form a sandwich structurewhile sandwiching M. Here, the substituted cyclopentadienyl group refersto an indenyl group, a fluorenyl group, an azulenyl group, or any one ofthese groups, in which at least one hydrocarbyl group orsilicon-containing group is included as a substituent. In the case wherethe substituted cyclopentadienyl group is the indenyl group, thefluorenyl group, or the azulenyl group, a part of double bonds of anunsaturated ring condensed to the cyclopentadienyl group may behydrogenated. In the general formula [II], Y represents a divalenthydrocarbon group having the carbon number of 1 to 20, a divalenthalogenated hydrocarbon group having the carbon number of 1 to 20, adivalent silicon-containing group, a divalent germanium-containinggroup, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO₂—,—Ge—, —Sn—, —NR^(a)—, —P(R^(a))—, —P(O)(R^(a))—, —BR^(a)—, or —AlR^(a)—(where R^(a) represents a hydrocarbon group having the carbon number of1 to 20, a halogenated hydrocarbon group having the carbon number of 1to 20, a hydrogen atom, a halogen atom, or a nitrogen compound residue,in which a nitrogen atom is bonded to one or two hydrocarbon groupshaving the carbon number of 1 to 20 while the two may be the same ordifferent).

The metallocene compound favorably used in the present invention is across-linked metallocene compound represented by the following generalformula [III] disclosed by the present applicant in InternationalPublication No. 01/27124 among the cross-linked metallocene compoundsrepresented by the above-described general formula [II]. Thepolymerization catalyst used in the present invention is a metallocenecatalyst composed of a cross-linked metallocene compound represented bythe general formula [III], an organometallic compound, anorganoaluminumoxy compound, a compound capable of forming an ion pairthrough reaction with a metallocene compound and, in addition, aparticulate carrier, as necessary.

In the above-described general formula [III], R¹ to R¹⁴ representindividually a hydrogen atom, a hydrocarbon group, or asilicon-containing group, while they may be the same or different. Here,examples of hydrocarbon groups include straight chain hydrocarbongroups, e.g., a methyl group, an ethyl group, a n-propyl group, an allylgroup, a n-butyl group, a n-pentyl group, a hexyl group, a n-heptylgroup, a n-octyl group, a n-nonyl group, and a n-decanyl group; branchedhydrocarbon groups, e.g., an isopropyl group, a t-butyl group, an amylgroup, a 3-methyl pentyl group, a 1,1-diethyl propyl group, a1,1-dimethyl butyl group, a 1-methyl-1-propyl butyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methyl propyl group, and a1-methyl-1-isopropyl-2-methyl propyl group; cyclic saturated hydrocarbongroups, e.g., a cyclopentyl group, a cyclohexyl group, a cycloheptylgroup, a cyclooctyl group, a norbornyl group, and an adamantyl group;cyclic unsaturated hydrocarbon groups, e.g., a phenyl group, a tolylgroup, a naphthyl group, a biphenyl group, a phenanthryl group, and ananthracenyl group; saturated hydrocarbon groups including cyclicunsaturated hydrocarbon groups, e.g., a benzyl group, a cumyl group, a1,1-diphenyl ethyl group, and a triphenyl methyl group, as substituents;and hetero atom-containing hydrocarbon groups, e.g., a methoxy group, anethoxy group, a phenoxy group, a furyl group, a N-methylamino group, aN,N-dimethylamino group, a N-phenylamino group, a pyrryl group, and athienyl group. Examples of silicon-containing groups include atrimethylsilyl group, a triethylsilyl group, a dimethylphenylsilylgroup, a diphenylmethylsilyl group, and a triphenylsilyl group. In thisregard, adjacent groups among R⁵ to R¹² may be mutually bonded to form aring. Specific examples of substituted fluorenyl groups having R⁵ to R¹²include a benzofluorenyl group, a dibenzofluorenyl group, anoctahydrodibenzofluorenyl group, an octamethyloctahydrodibenzofluorenylgroup, and an octamethyltetrahydrodicyclopentafluorenyl group.

In the general formula [III], R¹ to R⁴ bonded to a cyclopentadienyl ringas substituents are preferably a hydrogen atom or a hydrocarbon grouphaving the number of carbon atoms of 1 to 20. More preferably, R² and R⁴are a hydrocarbon group having the number of carbon atoms of 1 to 20.Particularly preferably, R¹ and R³ are a hydrogen atom, and R² and R⁴are a straight chain or branched alkyl group having the number of carbonatoms of 1 to 5.

In the general formula [III], R⁵ to R¹² bonded to a fluorene ring assubstituents are preferably a hydrogen atom or a hydrocarbon grouphaving the number of carbon atoms of 1 to 20. Examples of hydrocarbongroups having the number of carbon atoms of 1 to 20 include the samehydrocarbon groups as those described above. Adjacent groups among R⁵ toR¹² may be mutually bonded to form a ring, R⁶ and R⁷ are preferably afluorene ring, where the two are not hydrogen atoms at the same time,and R¹⁰ and R¹¹ are preferably a fluorene ring, where the two are nothydrogen atoms at the same time.

In the general formula [III], Y cross-liking the cyclopentadienyl ringand the fluorenyl ring is a group 14 element, and preferably a carbonatom, a silicon atom, or a germanium atom, and more preferably a carbonatom.

Furthermore, R¹³ and R¹⁴ bonded to Y as substituents are individually ahydrocarbon group having the number of carbon atoms of 1 to 20,preferably an alkyl group having the number of carbon atoms of 1 to 3 oran aryl group having the number of carbon atoms of 6 to 20, and morepreferably a methyl group, an ethyl group, a phenyl group, or a tolylgroup. The groups R¹³ and R¹⁴ may be the same or different and may bebonded to each other to form a ring. Moreover, R¹³ and R¹⁴ may be bondedto an adjacent group among R⁵ to R¹² or an adjacent group among R¹ to R⁴to form a ring.

In the general formula [III], M represents a group 4 transition metal,and preferably a titanium atom, a zirconium atom, or a hafnium atom, Qrepresents a halogen atom, a hydrocarbon group, or a group selected froman anionic ligand and a neutral ligand capable of coordinating with alone electron pair, and j represents an integer of 1 to 4. In the casewhere j is 2 or more, Qs may be mutually the same or different. As forthe halogen atom, a fluorine atom, a chlorine atom, a bromine atom, andan iodine atom are mentioned, and specific examples of the hydrocarbongroups include the same groups as those described above. Specificexamples of anionic ligands include alkoxy groups of methoxy, t-butoxy,phenoxy, and the like; carboxylate groups of acetate, benzoate, and thelike; and sulfonate groups of mesylate, tosylate, and the like. Specificexamples of neutral ligands capable of coordinating with a lone electronpair include organic phosphorus compounds, e.g., trimethyl phosphine,triethyl phosphine, triphenyl phosphine, and diphenylmethyl phosphine;and ethers, e.g., tetrahydrofuran, diethyl ether, dioxane, and1,2-dimethoxyethane. It is preferable that at lest one of Qs is ahalogen atom or an alkyl group.

Examples of cross-linked metallocene compounds favorably used in thepresent invention includedimethylmethylene(3-t-butyl-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconiumdichloride,1-phenylethylidene(4-t-butyl-2-methylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride, and[3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)]zirconiumdichloride.

As for the organometallic compound, the organoaluminumoxy compound, andthe compound capable of forming an ion pair through reaction with themetallocene compound (cocatalyst) and, in addition, the particulatecarrier which is used as necessary, used together with the metallocenecompound represented by the general formula [III], the above-describedcompounds disclosed in International Publication No. 01/27124 andJapanese Unexamined Patent Application Publication No. 11-315109 can beused with no specific limitation.

In a manufacturing example, as described later, in the examplesaccording to the present invention, a propylene homopolymer is producedby performing prepolymerization in the copresence of[3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)]zirconiumdichloride, which serves as the metallocene compound represented by thegeneral formula (III) and which is represented by the following formula(A), and a solid catalyst, in which methylaluminoxane is held by asilica carrier, and triethylaluminum serving as cocatalysts, andsubsequently performing polymerization composed of a plurality ofstages.

The polymerization method is not specifically limited. For example,homopolymerization, copolymerization, multistage polymerization, and thelike are used.

In the case where the polypropylene based resin is used as thethermoplastic resin (A1) according to the present invention, for thepurpose of improving the impact resistance, an elastomer may be added,as necessary, and a form of polypropylene based resin composition may beemployed in the use. Examples of elastomers include propylene-α-olefincopolymers, ethylene-α-olefin nonconjugated polyene random copolymers,hydrogenated block copolymers, other elastomeric polymers, e.g.,ethylene-α-olefin random copolymer, and mixtures thereof. As for theα-olefin, the same α-olefins as the above-described α-olefins toconstitute the polyolefin based resin can be used. One type thereof maybe used alone, or at least two types may be used in combination.

As for the method for manufacturing the above-described polypropylenebased resin composition, a physical blending method, for example, amelt-blending method, is mentioned. The melt-blending method is a methodfor performing mechanical kneading while heating and plasticization areperformed by using a mixing roll, a Banbury mixer, a uniaxial or biaxialextruder, or the like.

Alternatively, in the case where the above-described polypropylene basedresin composition is composed of a polypropylene based resin and apropylene-α-olefin copolymer, production may be performed in the form ofproduction of a propylene-α-olefin block copolymer besides theproduction by the physical blending method. The production of thepropylene-α-olefin block copolymer is performed by continuouslyconducting the following two steps (Step 1 and Step 2).

[Step 1] A step to produce a propylene homopolymer or apropylene-α-olefin copolymer by (co)polymerizing propylene and, asnecessary, at least one type of olefin selected from ethylene andα-olefins having the carbon number of 4 or more in the presence of ametallocene compound-containing catalyst.[Step 2] A step to produce a propylene-α-olefin copolymer containingethylene and the α-olefin having the carbon number of 4 or more at acontent larger than that in Step 1 by copolymerizing propylene and atleast one type of olefin selected from ethylene and α-olefins having thecarbon number of 4 or more in the presence of a metallocenecompound-containing catalyst.

As for the thermoplastic resin (A1) according to the present invention,one type of the above-described resins may be used alone, or at leasttwo types may be used in combination.

The melting point of a resin component in the long-fiber-reinforcedthermoplastic resin particles (A) is 150° C. or higher, preferably 150°C. to 163° C., and more preferably 156° C. to 162° C. If the meltingpoint is lower than 150° C., the crystallinity is reduced and mechanicalstrength, e.g., bending strength at room temperature, may be reduced. Inthis regard, most of the above-described resin component is thethermoplastic resin (A1).

The melt index (MI; resin temperature 230° C., load 21.18 N) ofthermoplastic resin (A1) is preferably 100 to 250 g/10 min, as in theitem (a-1), and more preferably 100 to 150 g/10 min. In the case wherethe melt index of the thermoplastic resin (A1) is within theabove-described range, during production of the long-fiber-reinforcedthermoplastic resin particles (A) described later, the reinforcingfibers (A3) are impregnated with the thermoplastic resin (A1) easilyand, thereby, the long-fiber-reinforced thermoplastic resin particles(A) with improved dispersibility of the reinforcing fibers (A3) isobtained. Therefore, if the melt index of the thermoplastic resin (A1)is less than 100 g/10 min, the reinforcing fibers may become difficultto open during molding. On the other hand, if the melt index of thethermoplastic resin (A1) exceeds 250 g/10 min, the strength of thelong-fiber-reinforced thermoplastic resin particles (A) may be reduced.

In order to control the melt index of the thermoplastic resin (A1)within the above-described range, for example, the molecular weight maybe adjusted by controlling the concentration of hydrogen introducedduring the polymerization and the like, decomposition may be effectedwith a peroxide, or resins having different melt indexes may be blendedor kneaded in the production of the thermoplastic resin (A1).

The amount of components soluble into o-dichlorobenzene at 90° C.measured by cross fractionation chromatography (CFC method) of thethermoplastic resin (A1) is preferably 1 percent by weight or less, asin the item (a-2), more preferably 0.5 percent by weight or less, andparticularly preferably 0.3 percent by weight or less. The amount ofelution at 90° C. or lower of 1 percent by weight or less refers to thatthe content of low-crystallinity and low-molecular weight componentsamong polymer components constituting the thermoplastic resin (A1) issmall and refers to that the thermoplastic resin (A1) has high heatresistance and high strength.

The present inventors produced a thermoplastic resin by using a Zieglerbased catalyst, as described in Japanese Patent Application No.2008-074405. Regarding the thermoplastic resin produced by using theZiegler based catalyst, the amount of elution at 90° C. is about 3 to 10percent by weight. That is the thermoplastic resin produced by using theZiegler based catalyst has a larger content of low-crystallinity,low-molecular weight components and exhibits poor heat resistance andlow strength as compared with the thermoplastic resin (A1) according tothe present invention.

The thermoplastic resin (A1) according to the present invention ischaracterized in that decomposition through addition of a peroxide isnot necessary prior to production of the long-fiber-reinforcedthermoplastic resin particles (A) because the molecular weightdistribution (Mw/Mn) is made narrow due to characteristics of themetallocene catalyst and, therefore, the production step is efficientand almost no volatile organic compound (VOC) is generated in adecomposition step and the like due to addition of a peroxide.

The molecular weight distribution (Mw/Mn) in terms of standardpolypropylene, measured by gel permeation chromatography (GPC) of thethermoplastic resin (A1), is preferably less than 3.5, as in the item(a-3), more preferably 1.5 to 3, and particularly preferably 2 to 2.7.If the molecular weight distribution (Mw/Mn) is 3.5 or more, the openingproperty of fibers during production of the long-fiber-reinforcedthermoplastic resin particles (A) is degraded, lump-shaped poorappearance may occur on the surface of a molded body obtained by moldingthe long-fiber-reinforced thermoplastic resin particles (A).Furthermore, the number average molecular weight (Mn) is usually 2×10⁴to 12×10⁴, preferably 3×10⁴ to 10×10⁴, and more preferably 4×10⁴ to8×10⁴. The number average molecular weight (Mn) within theabove-described range is favorable from the viewpoint of ensuringcompatibility between an operating ease in fiber impregnation step andmechanical strength.

Regarding the content of the thermoplastic resin (A1), the thermoplasticresin (A1) and the modified polyolefin resin (A2) constitute 20 to 70percent by weight, preferably 25 to 67 percent by weight, and morepreferably 30 to 65 percent by weight in 100 percent by weight of thetotal of the thermoplastic resin (A1), the modified polyolefin resin(A2), and the reinforcing fibers (A3).

Furthermore, the content of the thermoplastic resin (A1) is preferably25 to 59 percent by weight, more preferably 30 to 57 percent by weight,and particularly preferably 35 to 55 percent by weight in 100 percent byweight of the total of the thermoplastic resin (A1), the modifiedpolyolefin resin (A2), and the reinforcing fibers (A3). If the contentof the thermoplastic resin (A1) is less than 25 percent by weight,impregnation of the fiber may be reduced. On the other hand, if thecontent of the thermoplastic resin (A1) exceeds 59 percent by weight,production of the long-fiber-reinforced thermoplastic resin particles(A) according to the present invention may become difficult.

<Modified Polyolefin Resin (A2)>

The modified polyolefin resin (A2) modified with an unsaturatedcarboxylic acid or a derivative thereof, according to the presentinvention, has a functional group, e.g., a carboxyl group or acarboxylic acid anhydride group, in the polyolefin resin.

The type of the polyolefin resin to be modified is not specificallylimited, and it is preferable that the same polyolefin resins as thosedescribed above for the thermoplastic resin (A1) are used. For example,in the case where a polypropylene based resin is used as thethermoplastic resin (A1), it is preferable that a modified polypropylenebased resin is used as the modified polyolefin resin (A2).

In this regard, examples of modified polyolefin resins (A2) includemodified propylene homopolymers, modified propylene-α-olefin randomcopolymers, and modified propylene-α-olefin block copolymers.

As for the method for modifying the polyolefin resin, graft modificationand copolymerization can be employed.

Examples of unsaturated carboxylic acids used for modification includeacrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid,itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconicacid, angelic acid, and phthalic acid. Furthermore, as for thederivatives thereof, acid anhydrides, esters, amides, imides, metalsalts, and the like are mentioned. Examples thereof include maleicanhydride, itaconic acid anhydride, citraconic acid anhydride, nadicacid anhydride, phthalic anhydride, methyl acrylate, methylmethacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethylester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide,sodium acrylate, and sodium methacrylate. Among them, unsaturateddicarboxylic acids and derivatives thereof are preferable. Inparticular, maleic anhydride and phthalic anhydride are preferable.

The amount of modification of the unsaturated carboxylic acid or aderivative thereof is 0.01 to 2 percent by weight, preferably 0.05 to1.8 percent by weight, and more preferably 0.1 to 1.5 percent by weightin 100 percent by weight of the total of the thermoplastic resin (A1)and the modified polyolefin resin (A2).

Furthermore, the amount of addition of carboxylic acid in the modifiedpolyolefin resin (A2) is usually 0.1 to 14 percent by weight, andpreferably 0.8 to 8 percent by weight. The amount of addition of acid isdetermined from the area of a peak at 1,670 to 1,810 cm⁻¹ on the basisof measurement of the IR spectrum of the modified polyolefin resin.

The modification of the polyolefin resin may be performed prior to theproduction of the long-fiber-reinforced thermoplastic resin particles(A) or be performed during the melt-kneading process in the productionof the particles (A) concerned.

For example, in the case where the modification is performed prior tothe production of the above-described particles (A), when thelong-fiber-reinforced thermoplastic resin particles (A) are prepared, anappropriate amount of acid-modified polyolefin resin or the like isadded to the thermoplastic resin (A1).

In the case where the modification is performed during the melt-kneadingprocess, the thermoplastic resin (A1), the polyolefin resin, and theunsaturated carboxylic acid or a derivative thereof are kneaded in anextruder by using an organic peroxide and, thereby, the polyolefin resinis modified through graft copolymerization with the unsaturatedcarboxylic acid or a derivative thereof.

In this regard, examples of the above-described organic peroxides caninclude benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile,dicumyl peroxide, t-butyl hydroperoxide, α,α′-bis(t-butyl peroxydiisopropyl)benzene, bis(t-butyldioxy isopropyl)benzene,2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, and cumene hydroperoxide.

The content of the modified polyolefin resin (A2) is preferably 1 to 5percent by weight, and more preferably 1.5 to 3.5 percent by weight in100 percent by weight of the total of the thermoplastic resin (A1), themodified polyolefin resin (A2), and the reinforcing fibers (A3). If thecontent of the modified polyolefin resin (A2) is less than 1 percent byweight, interfacial adhesion between the fibers and the resin is reducedand the strength may be reduced. On the other hand, if the content ofthe modified polyolefin resin (A2) exceeds 5 percent by weight, themolecular weight of the whole becomes small and the strength may bereduced.

Furthermore, it is preferable that the thermoplastic resin (A1)constitutes 75 to 99 percent by weight and the modified polyolefin resin(A2) constitutes 1 to 25 percent by weight in 100 percent by weight ofthe total of the thermoplastic resin (A1) and the modified polyolefinresin (A2), and it is more preferable that the thermoplastic resin (A1)constitutes 85 to 98 percent by weight and the modified polyolefin resin(A2) constitutes 2 to 15 percent by weight.

<Reinforcing Fibers (A3)>

The reinforcing fibers (A3) according to the present invention is notspecifically limited. Examples thereof include organic fibers, e.g.,carbon and nylon, and inorganic fibers, e.g., basalt and glass fibers.Preferably, glass fibers are mentioned.

Examples of glass fibers can include E glass (Electrical glass), C glass(Chemical glass), A glass (Alkali glass), S glass (High strength glass),and filament-shaped fibers produced by melt-spinning glass, e.g.,alkali-resistant glass.

In the present invention, usually, glass long fibers are used. As forthe material for the glass long fibers, continuous glass fiber bundle isused. This is commercially available as a glass roving. The averagefiber diameter thereof is usually 3 to 30 μm, preferably 13 to 20 μm,and further preferably 16 to 18 μm. The number of filaments in a bundleis usually 400 to 10,000, preferably 1,000 to 6,000, and furtherpreferably 3,000 to 5,000.

Alternatively, a plurality of fiber bundles can be tied and used asdescribed in Japanese Unexamined Patent Application Publication No.6-114830.

The fiber lengths of glass fibers in the long-fiber-reinforcedthermoplastic resin particles (A) are usually 4 to 10 mm, and preferably5 to 8 mm, and the fiber diameters are usually 10 to 20 μm, andpreferably 13 to 18 μm.

The content of the reinforcing fibers (A3) is 30 to 80 percent byweight, preferably 40 to 70 percent by weight, more preferably 45 to 65percent by weight, and particularly preferably 45 to 60 percent byweight in 100 percent by weight of the total of the thermoplastic resin(A1), the modified polyolefin resin (A2), and the reinforcing fibers(A3). If the content of the reinforcing fibers (A3) is less than 30percent by weight, and more definitely less than 40 percent by weight,the productivity may be reduced. On the other hand, if the content ofthe reinforcing fibers (A3) exceeds 80 percent by weight, and moredefinitely 70 percent by weight, the amount of glass fibers increases,so that impregnation of the fibers is reduced and unopened glass fibersmay increase.

The content of the reinforcing fibers (A3) contained in the resinparticle blend (C) according to the present invention is 20 to 60percent by weight, preferably 25 to 40 percent by weight in 100 percentby weight of the total of the long-fiber-reinforced thermoplastic resinparticles (A) and the polyolefin resin particles (B) for dilution. Ifthe content of the reinforcing fibers (A3) is less than 20 percent byweight, the strength of the resulting molded body may becomeinsufficient. If the content of the reinforcing fibers (A3) exceeds 60percent by weight, the appearance may become poor.

The surfaces of the reinforcing fibers (A3) can be provided withfunctional groups by various surface treatment methods, e.g., anelectrolytic treatment and a sizing agent treatment. It is preferablethat a sizing agent is used for the surface treatment, and it isparticularly preferable that a sizing agent containing a coupling agentis used. In the case where the thus surface-treated reinforcing fibersare used, the adhesion to the thermoplastic resin (A1) is improved and amolded body having good strength and appearance is obtained.

Examples of sizing agents include those containing coupling agentsdescribed in Japanese Unexamined Patent Application Publication No.2003-253563.

The coupling agent can be selected from previously known couplingagents, e.g., so-called silane based coupling agents, such asaminosilane and epoxysilane, and titanium based coupling agents.

Furthermore, sizing agents containing a resin emulsion to facilitatehandling, besides the coupling agent, are also preferable.

As for the resin emulsion contained in the sizing agent, urethane based,olefin based, acryl based, nylon based, butadiene based, and epoxy basedemulsions and the like can be used. Among them, urethane based andolefin based emulsions are used preferably. Here, as for the urethanebased sizing agent, usually, any one of one-component types, e.g.,oil-modified type, moisture-curing type, and block type, andtwo-component types, e.g., catalyst-curing type and polyol-curing type,can be used insofar as the agent contains polyisocyanate obtained by apolyaddition reaction between a diisocyanate compound and a polyhydricalcohol at a proportion of 50 percent by weight or more. Typicalexamples include VONDIC series and HYDRAN series (both produced by DICCorporation). On the other hand, as for the olefin based sizing agent,for example, modified polyolefin based resin modified with anunsaturated carboxylic acid or a derivative thereof can be used.

<Long-Fiber-Reinforced Thermoplastic Resin Particles (A)>

The long-fiber-reinforced thermoplastic resin particles (A) includingthe above-described thermoplastic resin (A1), the modified polyolefinresin (A2), and the reinforcing fibers (A3) can be produced by apublicly known molding method, e.g., a drawing method. A part of thethermoplastic resin (A1), the modified polyolefin resin (A2), and thereinforcing fibers (A3) may be melt-kneaded separately and, thereafter,mixing (blending) may be performed.

The shapes of the long-fiber-reinforced thermoplastic resin particles(A) are usually columnar.

The particle lengths of the long-fiber-reinforced thermoplastic resinparticles (A) are usually 4 to 10 mm, and preferably 5 to 8 mm. If theparticle lengths of the long-fiber-reinforced thermoplastic resinparticles (A) are less than 4 mm, effects of improving the rigidity, theheat resistance, and the impact resistance may be low, and the curvaturedeformation may increases. On the other hand, if the particle lengths ofthe long-fiber-reinforced thermoplastic resin particles (A) exceed 10mm, molding may be difficult.

Furthermore, it is preferable that the reinforcing fibers (A3) havingfiber lengths of 4 to 10 mm are aligned in almost parallel in thelong-fiber-reinforced thermoplastic resin particles (A).

Regarding the long-fiber-reinforced thermoplastic resin particles (A)according to the present invention, the aspect ratio of the reinforcingfibers (A3) is large in the particles (A), so that the resin blend (C)having high strength is obtained easily.

The long-fiber-reinforced thermoplastic resin particles (A) can beobtained easily by leading a roving of the reinforcing fibers (A3)composed of several thousands of fibers to an impregnation dice,impregnating between fibers with molten thermoplastic resin (A1) andmodified polyolefin resin (A2) (hereafter may be simply referred to as“molten resins”) uniformly and, thereafter, performing cutting into arequired length.

For example, a method in which the molten resins are fed from anextruder into an impregnation dice disposed at the end of the extruderwhile a continuous glass fiber bundle is passed to impregnate the glassfiber bundle with the molten resins and, thereafter, drawing isperformed through a nozzle, and pelletizing into a required length isperformed is employed. Alternatively, a method in which a polyolefinresin and an unsaturated carboxylic acid or an anhydride thereof aredry-blended by using an organic peroxide, are put into a hopper of anextruder, and are fed while modification is effected at the same time isemployed as well.

The method for impregnation is not specifically limited. Any one of amethod in which a roving is passed through a resin powder fluidized bedand, thereafter, heating to the melting point of the resin or higher isperformed (Japanese Unexamined Patent Application Publication No.46-4545), a method in which a roving of reinforcing fibers isimpregnated with a molten thermoplastic resin by using a cross-head die(Japanese Unexamined Patent Application Publication No. 62-60625,Japanese Unexamined Patent Application Publication No. 63-132036,Japanese Unexamined Patent Application Publication No. 63-264326, andJapanese Unexamined Patent Application Publication No. 1-208118), amethod in which resin fibers and a roving of reinforcing fibers arewoven together and, thereafter, heating to the melting point of theresin or higher is performed to effect impregnation with the resin(Japanese Unexamined Patent Application Publication No. 61-118235), amethod in which a plurality of rods are disposed in the inside of a die,a roving is wrapped around them in a zigzag manner to open fibers andeffect impregnation with the molten resins (Japanese Unexamined PatentApplication Publication No. 10-264152), and a method in which passingbetween a pair of fiber opening pins without contacting the pins isperformed (International Publication No. 97/19805), and the like can beemployed.

Alternatively, in a process for melting a resin, an extruder having atleast two feed portions may be used, a decomposition agent may be put infrom a top feed, and another resin may be put in from a side feed. Atthis time, in the case of, for example, a polypropylene based resin, anorganic peroxide is preferable as the decomposition agent.

Alternatively, at least two extruders (extrusion portions) may be used,and a decomposition agent may be put into at least one of them.

Furthermore, a resin, un unsaturated carboxylic acid or a derivativethereof, and a decomposition agent may be put into at least one place ofan extruder.

Regarding the long-fiber-reinforced thermoplastic resin particles (A)obtained as described above, when 25 g of the long-fiber-reinforcedthermoplastic resin particles (A) are encapsulated in a 20-L SUS chamberand are stood at 65° C. for 1 hour, the amount of acetaldehydedissipated from the particles (A) concerned is 3.0 μg/m³ or less,preferably 2.8 μg/m³ or less, and more preferably 2.7 μg/m³ or less.

As described above, the thermoplastic resin (A1) according to thepresent invention has a narrow molecular weight distribution (Mw/Mn) dueto characteristics of the metallocene catalyst used in the productionand, therefore, decomposition of the thermoplastic resin (A1) throughaddition of a peroxide is not necessary prior to production of thelong-fiber-reinforced thermoplastic resin particles (A). The amount ofacetaldehyde dissipated from the particles (A) is small because volatilelow-molecular weight components in association with decomposition due tothe peroxide are not generated.

Therefore, in the present invention, an operation to remove volatilecomponents (VOC and the like) generated in association withdecomposition of the thermoplastic resin (A1) is unnecessary, so thatthe long-fiber-reinforced thermoplastic resin particles (A) can beproduced efficiently.

In this regard, the thermoplastic resin described in Japanese PatentApplication No. 2008-074405 is produced by using a Ziegler basedcatalyst, so that the molecular weight distribution (Mw/Mn) is wide andmuch low-molecular weight components are contained. Consequently,decomposition through addition of a peroxide is necessary prior toproduction of the long-fiber-reinforced thermoplastic resin particles(A). Therefore, in the case where 25 g of pellets formed from thethermoplastic resin produced by using the Ziegler based catalyst areanalyzed, the amount of acetaldehyde results in 6.7 μg/m³ and the amountof dissipation of aldehyde is obviously larger than that of thelong-fiber-reinforced thermoplastic resin particles (A) according to thepresent invention.

The content of the long-fiber-reinforced thermoplastic resin particles(A) according to the present invention is 10 to 90 percent by weight,preferably 50 to 90 percent by weight, and more preferably 50 to 80percent by weight in 100 percent by weight of the total of thelong-fiber-reinforced thermoplastic resin particles (A) and thepolyolefin resin particles (B) for dilution.

[Polyolefin Resin Particles (B) for Dilution]

As for the polyolefin resin particles (B) for dilution according to thepresent invention, for example, polyethylene based resins, polypropylenebased resins, and the like can be used. More specific examples ofpolyethylene based resins include low-density polyethylene (LDPE) andethylene-α-olefin copolymers and examples of polypropylene based resinsinclude propylene homopolymers, propylene-α-olefin random copolymers,and propylene-α-olefin block copolymers. Among them, polypropylene basedresins are mentioned as particularly preferable resins.

As for the method for manufacturing the polyolefin resin particles (B)for dilution, publicly known manufacturing methods by using ametallocene catalyst, a Ziegler based catalyst, or the like can beemployed with no limitation. For example, manufacturing methodsdescribed in Japanese Unexamined Patent Application Publication No.11-071431, Japanese Unexamined Patent Application Publication No.2002-234976, Japanese Unexamined Patent Application Publication No.2002-249624, International Publication No. 01/27124 described above,Japanese Unexamined Patent Application Publication No. 11-315109described above, and the like can be employed.

The melt index (MI; resin temperature 230° C., load 21.18 N) of thepolyolefin resin particles (B) for dilution is preferably 20 to 70 g/10min, as in the item (b-1), and more preferably 20 to 60 g/10 min. In thecase where the melt index of the polyolefin resin particles (B) fordilution is within the above-described range, the viscosity of the resinblend (C) can be maintained at a high level and the shear stress can beincreased during injection molding of the resin blend (C). If the meltindex of the polyolefin resin particles (B) for dilution is less than 20g/10 min, the fluidity of the resin blend (C) may be reduced and moldtransfer may be reduced. On the other hand, if the melt index of thepolyolefin resin particles (B) for dilution exceeds 70 g/10 min, fiberunopening of glass fibers may increase.

In this regard, the method for controlling the melt index of thepolyolefin resin particles (B) for dilution within the above-describedrange is as described above with respect to the long-fiber-reinforcedthermoplastic resin particles (A).

The relaxation time λ=G′÷(G″×ω), that is, G′÷G″, is preferably 0.3seconds or shorter, where the angular frequency ω=1 (rad/sec), which iscalculated from the storage modulus G′ and the loss modulus G″ measuredwith a cone & plate rheometer (relaxation time λ≦0.3 sec), as in theitem (b-2). If the relaxation time λ exceeds 0.3 sec, fiber unopening ofglass fibers (A3) may increase or, for example, molding of a large scalemolded body for automobile may become difficult.

The relaxation time λ of the polyolefin resin particles (B) for dilutionis more preferably 0.01 to 0.3 sec, and particularly preferably 0.05 to0.28 sec. The relaxation time λ of 0.3 sec or shorter is favorablebecause the fluidity and the properties are kept in balance.

The relaxation time λ will be described below.

Regarding a material system which has reached a new equilibrium state orsteady state from an original equilibrium state by application of anexternal force, a relaxation phenomenon refers to a phenomenon in whichwhen the external force is removed, the system returns to the originalequilibrium state on the basis of an internal motion of the system. Thespecific time constant serving as a guidepost of the time required forrelaxation is referred to as a relaxation time. In the case where apolymer is molded, a molten polymer is allowed to flow. At this time,the molecular chain is drawn in the flow direction and is aligned (thisis referred to as “orient”). However, when the drawing is finished, theflowing is stopped, and cooling is started, the stress applied to themolecule is removed, and each molecular chain begins to move and pointsan arbitrary direction in the end (this is referred to as “relaxation ofmolecular chain”).

This relaxation time λ can be represented by

λ=G′/ωG″=G′/G″,

where the angular frequency w=100°=1 (rad/sec).

Here, G′ represents a storage modulus showing an elastic property of thepolyolefin resin, and G″ represents a loss modulus showing a viscousproperty of the polyolefin resin. As is clear from this formula, a long(large) relaxation time λ indicates that G′ is large, and there are muchcomponents exhibiting an elastic property in the polyolefin resin. Onthe other hand, a short (small) relaxation time λ indicates that G″ islarge and indicates that there are much components exhibiting a viscousproperty in the polyolefin resin, that is, the molecular weight of theresin is small and the molecular weight distribution is narrow.

As for the method for controlling the relaxation time, the followingmethods are mentioned.

(1) The molecular weight distribution is changed through decompositionwith a peroxide or the like (in particular, resins having small λ areobtained easily from a high molecular weight material throughdecomposition under high magnification).(2) A plurality of resins having different molecular weightdistributions are mixed (it is effective to produce resins having narrowmolecular weight distributions by a method in which, for example, thedegree of decomposition is increased by using a high-activity catalystor using large amounts of peroxide and combine the resins).(3) In multistage polymerization, individual polymerization conditionsare adjusted (however, it may be industrially disadvantageous from theviewpoint of the cost).(4) Selection of polymerization catalyst

The molecular weight distribution (Mw/Mn) in terms of standardpolypropylene measured by gel permeation chromatography (GPC) of thepolyolefin resin particles (B) for dilution is preferably 2.5 to 6.0, asin the item (b-3), more preferably 3.0 to 5.5, and particularlypreferably 3.5 to 5.5. The molecular weight (Mn) is usually 1×10⁴ to12×10⁴, preferably 2×10⁴ to 10×10⁴, and more preferably 3×10⁴ to 8×10⁴.The number average molecular weight (Mn) within the above-describedrange is favorable from the viewpoint of ensuring compatibility betweenan operating ease in fiber impregnation step and mechanical strength.

The content of the polyolefin resin particles (B) for dilution accordingto the present invention is 10 to 90 percent by weight, preferably 10 to50 percent by weight, and more preferably 20 to 50 percent by weight in100 percent by weight of the total of the long-fiber-reinforcedthermoplastic resin particles (A) and the polyolefin resin particles (B)for dilution.

[Long-Fiber-Reinforced Thermoplastic Resin Particle Blend (C)]

The resin blend (C) according to the present invention is formed fromthe long-fiber-reinforced thermoplastic resin particles (A) and thepolyolefin resin particles (B) for dilution. That is, the resin blend(C) according to the present invention is a dry blend material obtainedby physically dry-blending the long-fiber-reinforced thermoplastic resinparticles (A) and the polyolefin resin particles (B) for dilutionsubstantially. Here, the term “substantially” refers to that the resinblend (C) according to the present invention may contain the followingadditives in addition to the long-fiber-reinforced thermoplastic resinparticles (A) and the polyolefin resin particles (B) for dilution.

That is, additives, for example, reforming additives, e.g., a dispersingagent, a lubricant, a plasticizer, a flame retardant, an antioxidant(phenol based antioxidant, phosphorus based antioxidant, and sulfurbased antioxidant), an antistatic agent, a copper inhibitor, a lightstabilizer, an ultraviolet absorber, a crystallization promoter(nucleating agent), a foaming agent, a cross-linking agent, and anantimicrobial agent, coloring agents, e.g., pigments and dyes, granularfillers, e.g., carbon black, titanium oxide, red iron oxide, azopigments, anthraquinone pigments, phthalocyanine, talc, calciumcarbonate, mica, and clay, short-fiber shaped fillers, e.g.,Wollastonite, and whiskers, e.g., potassium titanate, may be contained.

These additives may be added in production of the long-fiber-reinforcedthermoplastic resin particles (A), so as to be contained in thelong-fiber-reinforced thermoplastic resin particles (A), or be added inproduction of a molded body.

The resin blend (C) according to the present invention is obtained byvarious publicly known methods, for example, by performing dry-blendingwith a V-type blender, a ribbon blender, a Henschel mixer, a tumblermixer, or the like. The production condition can be adjustedappropriately in accordance with, for example, the type of the materialused. It is desirable that, preferably, the long-fiber-reinforcedthermoplastic resin particles (A) and the polyolefin resin particles (B)for dilution are put into a tumbler blender and dry-blended within 3minutes under the condition of 50° C. or lower.

Regarding the resin blend (C) according to the present invention, it isdesirable that the long-fiber-reinforced thermoplastic resin particles(A) are X g, the polyolefin resin particles (B) for dilution are 50−X g,and the standard deviation (1σ) is within the range of usually 4.5 orless, preferably 3.5 or less, and more preferably 3.0 or less on anaverage value basis when five samples in an amount of 50 g are taken atrandom from the dry blend material obtained as described above andindividual weights are measured. The standard deviation within theabove-described range is favorable because the resin blend (C) accordingto the present invention is dispersed uniformly.

As described above, the resin blend (C) according to the presentinvention is the dry blend material formed form thelong-fiber-reinforced thermoplastic resin particles (A) and thepolyolefin resin particles (B) for dilution. In the case where the resinblend (C) is not passed through an extruder, but is fed directly to amolding machine, e.g., an injection molding machine, the fiber length ofreinforcing fibers (A3) in the resin blend (C) is maintained and highereffects of improving the rigidity, the impact resistance, and thedurability can be obtained. In this regard, it is preferable that 5 to60 percent by weight of reinforcing fibers (A3) are contained in 100percent by weight of the total of the long-fiber-reinforcedthermoplastic resin particles (A) and the polyolefin resin particles (B)for dilution, and it is more preferable that 10 to 50 percent by weightof reinforcing fibers (A3) are contained.

[Molded Body]

Various molded bodies can be produced by molding thelong-fiber-reinforced thermoplastic resin particles (A) or the resinblend (C) according to the present invention.

As for the molding method, publicly known molding methods, e.g., aninjection molding method, an extrusion method, a blow molding method, acompression molding method, an injection compression molding method, agas-assisted injection molding, and a foam injection molding, can beemployed without limitation. Most of all, the injection molding method,the compression molding method, and the injection compression moldingmethod are preferable, and in particular, the injection molding methodis preferable.

The resin blend (C) according to the present invention is produced bypreparing the long-fiber-reinforced thermoplastic resin particles (A) inadvance and performing dry blending of the long-fiber-reinforcedthermoplastic resin particles (A) and the polyolefin resin particles (B)for dilution in contrast to PTLs 3 and 4 described above, in which asingle type of pellets are produced by using the long-fiber-reinforcedresin composition prepared through melt-kneading of two types ofpropylene polymers and the reinforcing fibers. If thelong-fiber-reinforced thermoplastic resin particles (A) are notprepared, but all the thermoplastic resin (A1), the modified polyolefinresin (A2), the reinforcing fibers (A3), and the polyolefin resinparticles (B) for dilution are melt-kneaded in one operation, thedispersibility of the reinforcing fibers (A3) in the resulting moldedbody is poor. In the resin blend (C) according to the present invention,uniformized long-fiber-reinforced thermoplastic resin particles (A) andpolyolefin resin particles (B) for dilution are contained, and thedispersibility of the reinforcing fibers (A3) is good. In production ofthe long-fiber-reinforced thermoplastic resin particles (A) according tothe present invention, the thermoplastic resin (A1) having a high meltindex (MI) and a narrow molecular weight distribution (Mw/Mn) is usedand performs a function of improving the dispersibility of thereinforcing fibers (A3) in the particles (A), or the polyolefin having alow melt index (MI) and a relatively wide molecular weight distribution(Mw/Mn) is used as the polyolefin resin particles (B) for dilution andperforms a function of maintaining the viscosity of the resin blend (C)in an injection cylinder at a high level to increase a shear stressduring injection molding.

Consequently, the molded body obtained by injection-molding the resinblend (C) according to the present invention exhibits excellentappearance because the reinforcing fibers (A3) are opened sufficiently.Furthermore, the fiber length of the reinforcing fibers (A3) is keptover a long period and, thereby, properties higher than or equivalent tothose of the conventional product can be maintained.

EXAMPLES

The present invention will be more specifically described below withreference to the examples. However, the present invention is not limitedto these examples.

Various parameters in Tables were measured by the following methods.

[Melt Index (MI)]

The measurement was performed on the basis of JIS K 7210-1999 under thecondition of a resin temperature of 230° C. and a load of 21.18 N.

[Amount of Components Soluble into o-Dichlorobenzene at 90° C.]

The measurement was performed by using a cross fractionationchromatograph (CFC).

The analysis of components soluble into o-dichlorobenzene at eachtemperature was performed by using a cross fractionation chromatograph(CFC). The CFC measurement was performed by using the followingapparatus provided with a temperature rising elution fractionation(TREF) section to perform composition fractionation and a GPC section toperform molecular weight fractionation under the following condition,and the amounts at individual temperatures were calculated.

Measurement apparatus: Model CFC T-150A, produced by MitsubishiPetrochemical Co., Ltd.,

Column: Shodex AT-806MS (×3 units)

Dissolution liquid: o-dichlorobenzene

Flow rate: 1.0 ml/min

Sample concentration: 0.3 wt %/vol % (containing 0.1% BHT)

Amount of injection: 0.5 ml

Solubility: complete dissolution

Detector: infrared absorption spectrometry, 3.42μ(2924 cm⁻¹), NaCl plate

Elution temperature: 0° C. to 135° C., 28 fractions

0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100,103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (° C.)

Regarding detailed measurement, a sample was dissolved by heating at145° C. for 2 hours and was kept at 135° C. Thereafter, the temperaturewas lowered to 0° C. at 10° C./hour, followed by keeping at 0° C. for 60minutes, so that coating with the sample was effected. The volume of thetemperature rising elution column was 0.83 ml, and the volume of thepipe was 0.07 ml. As for the detector, an infrared spectrometer ModelMIRAN 1A CVF (CaF₂ cell) produced by FOXBORO was used and infrared lightof 3.42μ (2924 cm⁻¹) was detected under the setting of an absorbancemode with a response time of 10 seconds. Regarding the elutiontemperature, 0° C. to 135° C. was divided into 28 fractions. Alltemperature are indicated in integers. For example, an elution fractionof 94° C. refers to components eluted at 91° C. to 94° C. The molecularweights of components not applied as a coating even at 0° C. andfractions eluted at individual temperatures were measured and molecularweights in terms of polypropylene were determined by using a universalcalibration curve. The SEC temperature was 135° C., the amount ofinjection of an internal standard was 0.5 ml, the position of injectionwas 3.0 ml, and the data sampling time was 0.50 seconds. Data processingwas performed with the analysis program “CFC Data Processing (version1.50)” attached to the apparatus.

[Number Average Molecular Weight (Mn), Weight Average Molecular Weight(Mw), and Molecular Weight Distribution (Mw/Mn)]

The measurement was performed by using a gel permeation chromatograph(GPC).

Regarding the measurement of the molecular weight and the molecularweight distribution, GPC-150C Plus produced by Waters Corporation wasused and the measurement was performed as described below. Theseparation columns were TSKgel GMH6-HT and TSK gel GMH6-HTL and eachcolumn size was an inside diameter of 7.5 mm and a length of 600 mm, thecolumn temperature was specified to be 140° C., o-dichlorobenzene (WakoPure Chemical Industries, Ltd.) was used as a mobile phase, and 0.025percent by weight of BHT (Wako Pure Chemical Industries, Ltd.) was usedas the antioxidant. Movement was performed at 1.0 ml/min, the sampleconcentration was specified to be 0.1 percent by weight, the amount ofinjection of the sample was specified to be 500 μL, and a differentialrefractometer was used as the detector. The standard polystyreneproduced by Tosoh Corporation was used where the molecular weightMw<1,000 and Mw>4×10⁶, the standard polystyrene produced by PressureChemical Company was used where 1,000≦Mw≦4×10⁶, and conversion to PP wasperformed by using a universal calibration method. In this regard, asfor the Mark-Houwink coefficients of PS and PP, the values described inliteratures (J. Polym. Sci., Part A-2, 8, 1803 (1970) and Makromol.Chem., 177, 213 (1976), respectively) were used.

[Measurement of Amount of VOC (acetaldehyde)]

The measuring method is as described below.

(i) A 20-L SUS chamber is brought into a hermetically sealed state andis heated to a temperature of 65° C.(ii) After 1 hour, the chamber blank is taken.(iii) After the chamber is returned to room temperature, thelong-fiber-reinforced thermoplastic resin particles (A) are put in andpurging with clean air is performed.(iv) The chamber is returned to the hermetically sealed state, and isheated to 65° C. again.(v) After standing in the hermetically sealed state for 1 hour, and aircontaining gases dissipated from the long-fiber-reinforced thermoplasticresin particles (A) is taken for 50 minutes at a sampling flow rate of200 mL/min while clean air is introduced again.

As for the absorbing agent, 2,4-DNPH cartridge was used.

(vi) 10 L of sampled gas is dissolved into a solvent, and aldehydescontained in the dissipated gas were analyzed by high performance liquidchromatography (HPLC).

In this regard, formaldehyde was also detected in association withaldehyde, but the amount of formaldehyde contained in the dissipated gastaken from 25 g of long-fiber-reinforced thermoplastic resin particles(A) was less than 2 μg/m³.

[Melting Point (Tm)]

The measurement was performed by using a differential scanningcalorimeter (DSC, produced by PerkinElmer, Inc.). Here, the endothermicpeak at the third step was defined as the melting point (Tm).

(Sample Preparation Condition)

Molding method: Press moldingMold: thickness 0.2 mm (a sample is sandwiched between aluminum foil andis press-molded by using a mold)Molding temperature: 240° C. (heating temperature 240° C.)Press pressure: 300 kg/cm², press time: 1 minuteAfter the press molding, the sheet is cooled with ice water and about0.4 g of sheet is encapsulated in the following containerMeasurement container: DSC PANS 10 μl BO-14-3015

DSC COVER B014-3003

(Measurement Condition)

First step: temperature is raised to 240° C. at 10° C./min and is keptfor 10 minutes.

Second step: temperature is lowered to 30° C. at 10° C./min.

Third step: temperature is raised to 240° C. at 10° C./min.

[Storage Modulus (G′), loss modulus (G″), and relaxation time (λ)]

(Sample Preparation Condition)

Molding method: press molding

Sample size: thickness: 1 mm, diameter: 2.8 mm

Molding condition:

Preheating: mold 200° C., 120 seconds while no pressure is applied

Degasification: mold 200° C., pressurization 0 to 30 kg/cm²→releasing isrepeated about 10 times as quick as possible

Pressurization: 60 seconds at a pressure of 80 kg/cm²

Cooling: cooling mold 30° C., 120 seconds at a pressure of 80 kg/cm²

The measurement was performed under the following condition by using acone & plate rheometer.

Measuring Apparatus: System-4 (trade name) Produced by Rheometrics

Shape of measurement section: cone & plate type

Measurement condition: 175° C., strain 30% (sine strain)

The storage modulus G′ and the loss modulus G″ were determined under theabove-described condition, and the relaxation time λ (sec), where anangular frequency (of sine strain applied to a circular plate) ω=1(rad/sec), was determined by calculating λ=G′÷(G″×ω)=G′÷G″.

By the way, the measurement with the cone & plate rheometer is describedin, for example, “SEIKEI KAKOU”, 1989, Vol. 1, No. 4, p. 355, “Koubunshijikkengaku (dai 9 kan) Rikigakutekiseishitsu 1 (Polymer Experimentology(Vol. 9) Dynamic Properties 1), KYORITSU SHUPPAN CO., LTD., 1982”, andJapanese Unexamined Patent Application Publication No. 2003-226791.

[Bending Test]

Test machine: Bend tester AGS-10KND produced by SHIMADZU CORPORATION

Test piece size: L×W×t=120×10×4 (mm)

Test condition: temperature 23° C., span 80 mm, test speed 2 mm/min

[Vibration Fatigue Characteristic]

A test piece having a width of 1.01 cm and a thickness of 0.27 cm wascut from the molded body obtained from the resin blend (C) according tothe present invention, and a vibration fatigue test was performed underthe condition of the frequency of 15 Hz and the temperatures of 23° C.and 90° C. with respect to the machine direction (MD) and the transversedirection (TD) of the test piece. The vibration test was performed undereach stress condition, and the vibration fatigability was evaluated onthe basis of the number of vibrations when the test piece was broken.

Production Example 1 Production of Thermoplastic Resin (A1) (mPP-1) (1)Production of Solid Catalyst Carrier

After 300 g of SiO₂ was sampled into a 1-L side-arm flask, 800 mL oftoluene was put in, and a slurry was produced. Subsequently, the liquidwas transferred to a 5-L four-necked flask, and 260 mL of toluene wasadded. Then, 2,830 mL of methylaluminoxane (hereafter may be referred toas “MAO”)-toluene solution (10 percent by weight solution) wasintroduced. Agitation was performed for 30 minutes while the temperaturewas kept at room temperature. The temperature was raised to 110° C. over1 hour, a reaction was effected for 4 hours. After the reaction wascompleted, cooling was performed to room temperature. After the cooling,a supernatant toluene was drawn, and substitution with fresh toluene wasperformed until the substitutional rate reached 95%.

(2) Production of Solid Catalyst (Supporting of Metal Catalyst Componentby Carrier)

In a glove box, 2.0 g of[3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)]zirconiumdichloride was weighed into a 5-L four-necked flask. The flask was takenout, 0.46 liters of toluene and 1.4 liters of MAO/SiO₂/toluene slurryprepared in the item (1) were added in nitrogen, and agitation wasperformed for 30 minutes to effect supporting. The resulting[3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)]zirconiumdichloride/MAO/SiO₂/toluene slurry was subjected to 99% substitutionwith n-heptane, so that the amount of final slurry was specified to be4.5 liters. This operation was performed at room temperature.

(3) Production of Prepolymerization Catalyst

An autoclave having an internal volume of 200 L provided with anagitator was charged with 404 g of solid catalyst component prepared inthe above-described item (2), 218 mL of triethylaluminum, and 100 L ofheptane, the internal temperature was kept at 15° C. to 20° C., 1,212 gof ethylene was put in, and a reaction was effected for 180 minuteswhile agitation was performed. After the polymerization was completed, asolid component was settled, and removal of a supernatant and washingwith heptane were performed two times. The resulting prepolymerizationcatalyst was suspended again in refined heptane, and adjustment withheptane was performed in such a way that the solid catalystconcentration became 4 g/L. The resulting prepolymerization catalystcontained 3 g of polyethylene in 1 g of solid catalyst component.

(4) Polymerization

A circulation type tubular polymerization device having an internalvolume of 58 L provided with a jacket was continuously supplied with 40kg/hour of propylene, 5 NL/hour of hydrogen, 0.8 g/hour, in terms ofsolid catalyst component, of the catalyst slurry produced in the item(3), and 4 ml/hour of triethylaluminum, and polymerization was effectedin a full liquid state, where no gas phase was present. The temperatureof the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 1,000 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 45 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.25 percentby mole. The polymerization was effected at a polymerization temperatureof 72° C. and a pressure of 3.1 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 500 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 10 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.25 percentby mole. The polymerization was effected at a polymerization temperatureof 71° C. and a pressure of 3.0 MPa/G.

The resulting slurry was vaporized and, thereafter, gas solid separationwas performed, so that a polypropylene homopolymer was obtained. Theresulting polypropylene homopolymer was vacuum-dried at 80° C.

Regarding the resulting polypropylene homopolymer, the number averagemolecular weight (Mn) was 42,000, the weight average molecular weight(Mw) was 93,000, the molecular weight distribution (Mw/Mn) was 2.2, themelt index (MI) was 165 g/10 min, the amount of elution at 90° C. orlower was 0.2 percent by weight, and the melting point (Tm) was 156° C.

The results are shown in Table 1.

Production Example 2 Production of Thermoplastic Resin (A1) (mPP-2)

A thermoplastic resin (mPP-2) was produced in a manner similar to thatin Production example 1 except that the polymerization in Productionexample 1 was changed to the following method.

(1) Polymerization

A circulation type tubular polymerization device having an internalvolume of 58 L provided with a jacket was continuously supplied with 40kg/hour of propylene, 5 NL/hour of hydrogen, 1.0 g/hour, in terms ofsolid catalyst component, of the catalyst slurry produced in the item(3) in Production example 1, and 4 ml/hour of triethylaluminum, andpolymerization was effected in a full liquid state, where no gas phasewas present. The temperature of the tubular reactor was 30° C., and thepressure was 3.2 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 1,000 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 45 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.24 percentby mole. The polymerization was effected at a polymerization temperatureof 72° C. and a pressure of 3.1 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 500 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 10 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.24 percentby mole. The polymerization was effected at a polymerization temperatureof 71° C. and a pressure of 3.0 MPa/G.

The resulting slurry was vaporized and, thereafter, gas solid separationwas performed, so that a polypropylene homopolymer was obtained. Theresulting polypropylene homopolymer was vacuum-dried at 80° C.

Regarding the resulting polypropylene homopolymer, the number averagemolecular weight (Mn) was 45,000, the weight average molecular weight(Mw) was 104,000, the molecular weight distribution (Mw/Mn) was 2.3, themelt index (MI) was 115 g/10 min, the amount of elution at 90° C. orlower was 0.1 percent by weight, and the melting point (Tm) was 156° C.

The results are shown in Table 1.

Production Example 3 Production of Thermoplastic Resin (mPP-3)

The following method was employed by using the solid catalyst carrierproduced in the item (1) in Production example 1.

(1) Production of Solid Catalyst (Supporting of Metal Catalyst Componentby Carrier)

In a glove box, 2.0 g ofdiphenylmethylene(3-t-butyl-5-methylcyclopentadienyl)(2,7-t-butylfluorenyl)zirconiumdichloride was weighed into a 5-L four-necked flask. The flask was takenout, 0.46 liters of toluene and 1.4 liters of MAO/SiO₂/toluene slurryprepared in the item (1) in Production example 1 were added in nitrogen,and agitation was performed for 30 minutes to effect supporting. Theresultingdiphenylmethylene(3-t-butyl-5-methylcyclopentadienyl)(2,7-t-butylfluorenyl)zirconiumdichloride/MAO/SiO₂/toluene slurry was subjected to 99% substitutionwith n-heptane, so that the amount of final slurry was specified to be4.5 liters. This operation was performed at room temperature.

(2) Production of Prepolymerization Catalyst

An autoclave having an internal volume of 200 L provided with anagitator was charged with 404 g of solid catalyst component prepared inthe above-described item (1), 218 mL of triethylaluminum, and 100 L ofheptane, the internal temperature was kept at 15° C. to 20° C., 606 g ofethylene was put in, and a reaction was effected for 180 minutes whileagitation was performed. After the polymerization was completed, a solidcomponent was settled, and removal of a supernatant and washing withheptane were performed two times. The resulting prepolymerizationcatalyst was suspended again in refined heptane, and adjustment withheptane was performed in such a way that the solid catalystconcentration became 4 g/L. The resulting prepolymerization catalystcontained 3 g of polyethylene in 1 g of solid catalyst component.

(3) Polymerization

A tubular polymerization device having an internal volume of 58 L wascontinuously supplied with 40 kg/hour of propylene, 5 NL/hour ofhydrogen, 1.7 g/hour, in terms of solid catalyst component, of thecatalyst slurry produced in the item (2) in Production example 3, and 4ml/hour of triethylaluminum, and polymerization was effected in a fullliquid state, where no gas phase was present. The temperature of thetubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 1,000 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 45 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.20 percentby mole. The polymerization was effected at a polymerization temperatureof 72° C. and a pressure of 3.1 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 500 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 10 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.20 percentby mole. The polymerization was effected at a polymerization temperatureof 71° C. and a pressure of 3.0 MPa/G.

The resulting slurry was transferred to a vessel polymerization devicehaving an internal volume of 500 L provided with an agitator and thepolymerization was further effected. The polymerization device wassupplied with 10 kg/hour of propylene and hydrogen in such a way thatthe hydrogen concentration in the gas phase portion became 0.20 percentby mole. The polymerization was effected at a polymerization temperatureof 69° C. and a pressure of 3.0 MPa/G.

Regarding the resulting polypropylene homopolymer (mPP-3), the numberaverage molecular weight (Mn) was 41,000, the weight average molecularweight (Mw) was 94,000, the molecular weight distribution (Mw/Mn) was2.3, the melt index (MI) was 165 g/10 min, the amount of componentssoluble into o-dichlorobenzene at 90° C. was 6 percent by weight, andthe melting point (Tm) was 147° C.

Example 1

Long-fiber-reinforced thermoplastic resin particles (A) were produced byusing the pellet manufacturing apparatus shown in FIG. 1.

In this regard, in FIG. 1, reference numeral 10 denotes a die, referencenumeral 20 denotes an extruder to supply a molten resin to the die 10,reference numeral 30 denotes a roll of a fiber bundle F, referencenumeral 40 denotes a tension roll group to give constant tension to thefiber bundle F pulled into the die 10, reference numeral 50 denotes acooling device to cool a molten resin-impregnated fiber bundle pulledout of the die 10, reference numeral 60 denotes a pull-out roll of thefiber bundle, and reference numeral 70 denotes a pelletizer to cut thepulled out molten resin-impregnated fiber bundle to producelong-fiber-reinforced thermoplastic resin particles (A). In thisapparatus, three fiber bundles F independent of each other areimpregnated with the molten resin at the same time.

The specific production condition is as described below.

Die: attachment to the end of a 50-mm diameter extruder while four rodsare disposed in an impregnation portion linearly

Fiber bundle: a glass roving in which 4,000 glass fibers (A3) having afiber diameter of 16 μm and having been surface-treated with aminosilaneare bundled

Preheating temperature: 200° C.

Thermoplastic resin (A1) and modified polyolefin resin (A2): mPP-1(propylene homopolymer) and PP-2 (maleic anhydride-modifiedpolypropylene, the amount of addition of maleic anhydride 2 percent byweight, H-1100P, produced by Prime Polymer Co., Ltd.) shown in Table 1are blended on the basis of the composition ratio shown in Table 2 andare melted

Melting temperature: 280° C.

Rod: four rods of 6 mm (diameter)×3 mm (length)

Inclination angle: 25 degrees

Under the above-described condition, the fiber bundles were fed into thedie with the tension roll group while the amount was adjusted, so as tobe impregnated. Thereafter, the fibers were pulled out of the die andwere cooled. Then, long-fiber-reinforced thermoplastic resin particles(A) having a particle length of 6 mm were prepared with the pelletizer.

The resulting particles (A) were dry-blended with PP-3 (propylenehomopolymer, polyolefin resin particles (B) for dilution) at the blendratio shown in Table 2 in such a way that the content of the glassfibers (A3) in the resulting resin blend (C) became 40 percent by weightand, thereby, the resin blend (C) was prepared.

Subsequently, test pieces of the long-fiber-reinforced thermoplasticresin particles (A) and the resin blend (C) were produced under thefollowing condition, and tests of bending strength [MPa] and bendingmodulus of elasticity [MPa] were performed.

Injection Molding Machine: FANUC α100B (Full-Flighted Screw)

Mold: ISO-compatible tensile dumbbell (family mold of 2 units)

Molding temperature: 250° C./45° C.

The results are shown in Table 2.

Then, the resulting resin blend (C) was introduced into an injectionmolding machine (AZ7000, produced by NISSEI PLASTIC INDUSTRIAL CO.,LTD.) and a tabular molded body of 200 mm×180 mm×3 mm was produced.

In this injection molding machine, a film gate was used as a mold, and afull-flighted screw was used as a screw. In this regard, molding wasperformed under the condition of the resin temperature of 250° C., themold temperature of 45° C., and the filling rate of 20 mm/sec.

A test piece was produced from the resulting molded body, and thevibration fatigue test was performed.

The results are shown in Tables 3 and 4. Tables 3 and 4 show the numberof vibrations, where the test piece was broken under each stresscondition.

FIGS. 2 to 5 are drawings of plots of the results shown in Tables 3 and4.

Furthermore, the number of unopening fiber portions of these moldedbodies were counted visually. In order to normalize these numbers, thenumber of unopening fibers in Example 1 was assumed to be 100, andratios of the numbers of unopening fibers of the molded bodies inExample 2 and Comparative example 1 thereto were determined as fiberunopening indices on the basis of the following formula.

fiber unopening index=(the number of unopening fibers)÷(the number ofunopening fibers in Example 1)×100

Example 2

Long-fiber-reinforced thermoplastic resin particles (A) and a resinblend (C) were prepared in a manner similar to that in Example 1 exceptthat mPP-2 shown in Table 1 was used as the thermoplastic resin (A1) inExample 1. The blend ratios of the individual components are shown inTable 2.

The resulting resin blend (C) was molded as in Example 1, so as toproduce a test piece.

The results of the vibration fatigue test are shown in Tables 3 and 4and FIGS. 2 to 5.

Comparative Example 1

Long-fiber-reinforced thermoplastic resin particles andlong-fiber-reinforced particle blend were prepared in a manner similarto that in Example 1 except that mPP-3 shown in Table 1 was used as thethermoplastic resin in Example 1. The blend ratios of the individualcomponents are shown in Table 2.

Comparative Example 2

Long-fiber-reinforced thermoplastic resin particles andlong-fiber-reinforced particle blend were prepared in a manner similarto that in Example 1 except that PP-1 shown in Table 1 was used as thethermoplastic resin in Example 1. The blend ratios of the individualcomponents are shown in Table 2.

In this regard, PP-1 was produced by adding 0.1 percent by weight ofbis(t-butyldioxyisopropyl)benzene (Perkadox 14, produced by Kayaku AkzoCorporation) serving as a peroxide to a propylene homopolymer (Y-6005GM,melt index (MI) 60, produced by Prime Polymer Co., Ltd.) and performingmelt-kneading. The melting point (Tm) of PP-1 (decomposition product ofY-6005GM) was 163° C.

The resulting long-fiber-reinforced particle blend was molded as inExample 1, so as to produce a test piece.

The results of the vibration fatigue test are shown in Tables 3 and 4and FIGS. 2 to 5.

It is clear that in Comparative example 1, the test piece is broken atthe number of vibrations smaller than those in Examples 1 and 2.Furthermore, the tendency was particularly remarkable in the case wherethe vibration fatigue test was performed at 90° C.

Comparative Example 3

For purposes of comparison with Example 1, a polyolefin resin wasproduced by melt-kneading all resin components contained in the resinblend (C) in Example 1, that is, mPP-1 (thermoplastic resin (A1)), PP-2(modified polyolefin resin (A2)), and PP-3 (polyolefin resin particles(B) for dilution), in one operation. Long-fiber-reinforced thermoplasticresin particles were produced by using the resulting polyolefin resin.The resulting long-fiber-reinforced thermoplastic resin particles wasused and molding was performed as in Example, so as to produce a testpiece. As a result, the dispersibility of glass fibers was significantlypoor as compared with Example 1, and many glass lumps due to poordispersion were generated.

TABLE 1 Thermoplastic Thermoplastic Thermoplastic Polyolefin resin resinresin resin Thermoplastic resin Modified polyolefin particles (B) for(A1) (mPP-1) (A1) (mPP-2) (mPP-3) (PP-1) resin (A2) (PP-2) dilution(PP-3) Type of polymer Propylene Propylene Propylene Propylene Maleicanhydride- Propylene homopolymer homopolymer homopolymer homopolymermodified homopolymer polypropylene Grade* A-1 A-2 A-3 DecompositionH-1100P J-3000GV product of Y-6005GM MI [g/10 min] 165 115 165 120 — 30Melting point (Tm) 156 156 147 163 — — [° C.] Amount of elution 0.2 0.16.0 6.5 — — at 90° C. or lower [percent by weight] λ [sec] — — — 0.03 —0.22 Mn (×10⁴) 4.2 4.5 4.1 4.3 3.7 Mw (×10⁴) 9.3 10.4 9.4 16.2 20.7 Mz(×10⁴) 16.6 18.7 16.5 45.3 72.9 Mw/Mn 2.2 2.3 2.3 3.8 5.5 Mz/Mw 1.8 1.81.8 2.8 3.5 *Everyone is produced by Prime Polymer Co., Ltd.

TABLE 2 Comparative Comparative Comparative Example 1 Example 2 example1 example 2 example 3 Long-fiber- Thermoplastic resin (A1) mPP-1 mPP-2mPP-3 PP-1 mPP-1 reinforced Modified polyolefin resin (A2) PP-2 PP-2PP-2 PP-2 PP-2 thermoplastic Content of modified polyolefin resin (A2)2.5 2.5 2.5 2.5 2.5 resin particles [percent by weight] (A)* Content ofglass fiber (A3) 50 50 50 50 40 [percent by weight] Melting point (Tm)[° C.] 156 156 147 163 156 Amount of acetaldehyde in dissipated gas 2.52.3 — 6.7 — [μg/g] Bending strength [MPa] 253 251 237 242 — Bendingmodulus of elasticity [MPa] 11,300 11,100 9,900 10,300 — Polyolefin PP-3PP-3 PP-3 PP-3 PP-3 resin particles (B) for dilution Long-fiber-Composition Long-fiber-reinforced 80 80 80 80 — reinforced ratiothermoplastic resin thermoplastic [percent by particles (A) resinparticle weight] Polyolefin resin particles 20 20 20 20 — blend (C) (B)for dilution Content of glass fiber (A3) [percent by 40 40 40 40 40weight] Molded body Bending strength [MPa] 168 — 159 162 160 Bendingmodulus of elasticity [MPa] 9,250 — 9,100 9,130 9100 Fiber unopeningindex 100 160 — 160 3000 *Total of thermoplastic resin (A1), modifiedpolyolefin resin (A2), and glass fiber (A3) is 100 percent by weight.

TABLE 3 Under condition of 23° C. Example 1 Example 2 Comparativeexample 2 Stress (MPa) MD TD MD TD MD TD 40 35 30 2,300 244 2,597 2182,386 50 25 11,272 1,272 12,965 1,304 5,403 304 20 323,764 17,509754,474 19,059 200,579 3,707 15 10,000,000 463,770 10,000,000 783,0910,000,000 134,150 10 10,000,000 10,000,000 10,000,000 5

TABLE 4 Comparative example Under condition of 90° C. Example 1 Example2 2 Stress (MPa) MD TD MD TD MD TD 40 35 30 231 20 600 37 136 5 2512,400 465 3,852 252 3,888 37 20 232,280 2,728 68,300 3,406 22,806 87415 9,219,511 107,482 10,000,000 340,641 3,643,249 34,203 10 10,000,000995,448 10,000,000 1,267,151 604,622 5

INDUSTRIAL APPLICABILITY

The molded body formed from the long-fiber-reinforced thermoplasticresin particles (A) or the Long-fiber-reinforced thermoplastic resinparticle blend (C) according to the present invention can be favorablyused for applications, e.g., automobile parts (front ends, fan shrouds,cooling fans, engine under covers, engine covers, radiator boxes, sidedoors, slide doors, back door inners, back door outers, outer panels,fenders, roof rails, door handles, door trims, luggage boxes, wheelcovers, and handles), two-wheeled vehicle•bicycle parts (luggage boxes,handles, and wheels), house parts (warm water cleaning toilet seatparts, bath room parts, bathtub parts, legs of chairs, valves, and meterboxes), washing machine parts (tubs, balance rings, and the like), fansfor wind turbine generators, power tool parts, mower handles, and hosejoints.

REFERENCE SIGNS LIST

-   -   10 die    -   20 extruder    -   30 roll of fiber bundle F    -   40 tension roll group    -   50 cooling device    -   60 pull-out roll    -   70 pelletizer

1. Long-fiber-reinforced thermoplastic resin particles (A) characterized by comprising a thermoplastic resin (A1) produced by using a metallocene catalyst, a modified polyolefin resin (A2) modified with an unsaturated carboxylic acid or a derivative thereof, and reinforcing fibers (A3), wherein the following requirements (1) to (5) are satisfied. (1) The amount of modification of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 2 percent by weight in 100 percent by weight of the total of the thermoplastic resin (A1) and the modified polyolefin resin (A2). (2) The total of the thermoplastic resin (A1) and the modified polyolefin resin (A2) constitute 20 to 70 percent by weight in 100 percent by weight of the total of the thermoplastic resin (A1), the modified polyolefin resin (A2), and the reinforcing fibers (A3). (3) The reinforcing fibers (A3) constitute 30 to 80 percent by weight in 100 percent by weight of the total of the thermoplastic resin (A1), the modified polyolefin resin (A2), and the reinforcing fibers (A3). (4) When 25 g of the long-fiber-reinforced thermoplastic resin particles (A) are encapsulated in a 20-L chamber and are stood at 65° C. for 1 hour, the amount of acetaldehyde dissipated from the long-fiber-reinforced thermoplastic resin particles (A) is 3.0 μg/m³ or less. (5) The melting point of the resin component in the long-fiber-reinforced thermoplastic resin particles (A) is 150° C. or higher.
 2. The long-fiber-reinforced thermoplastic resin particles (A) according to claim 1, characterized in that the thermoplastic resin (A1) constitutes 75 to 99 percent by weight and the modified polyolefin resin (A2) constitutes 1 to 25 percent by weight in 100 percent by weight of the total of the thermoplastic resin (A1) and the modified polyolefin resin (A2).
 3. The long-fiber-reinforced thermoplastic resin particles (A) according to claim 1, characterized in that the thermoplastic resin (A1)) satisfies the following requirements (a-1), (a-2), and (a-3). (a-1) The melt index (MI; resin temperature 230° C., load 21.18 N) is within the range of 100 to 250 g/10 min. (a-2) The amount of components soluble into o-dichlorobenzene at 90° C. measured by cross fractionation chromatography (CFC method) is 1 percent by weight or less. (a-3) The molecular weight distribution (Mw/Mn) is less than 3.5.
 4. The long-fiber-reinforced thermoplastic resin particles (A) according to claim 1, characterized in that the thermoplastic resin (A1) is at least one type of polymer selected from propylene homopolymers and propylene-α-olefin random copolymers.
 5. The long-fiber-reinforced thermoplastic resin particle dry blend material (C) characterized by comprising: 10 to 90 percent by weight of long-fiber-reinforced thermoplastic resin particles (A) according to claims 1, and 90 to 10 percent by weight of polyolefin resin particles (B) for dilution (where the total of the long-fiber-reinforced thermoplastic resin particles (A) and the polyolefin resin particles (B) for dilution is assumed to be 100 percent by weight).
 6. The long-fiber-reinforced thermoplastic resin particle dry blend material (C) according to claim 5, characterized in that the reinforcing fibers (A3) constitute 5 to 60 percent by weight in 100 percent by weight of the total of the long-fiber-reinforced thermoplastic resin particles (A) and the polyolefin resin particles (B) for dilution.
 7. The long-fiber-reinforced thermoplastic resin particle dry blend material (C) according to claim 5, characterized in that the polyolefin resin particles (B) for dilution satisfy the following requirements (b-1), (b-2), and (b-3). (b-1) The melt index (MI; resin temperature 230° C., load 21.18 N) is within the range of 20 to 70 g/10 min. (b-2) The relaxation time λ is 0.3 seconds or shorter, where the angular frequency ω=1 (rad/sec), which is calculated from the storage modulus G′ and the loss modulus G″ measured with a cone & plate rheometer. (b-3) The molecular weight distribution (Mw/Mn) is within the range of 2.5 to 6.0.
 8. A molded body produced through molding by using long-fiber-reinforced thermoplastic resin particles (A) according to claim
 1. 9. A molded body produced through molding by using long-fiber-reinforced thermoplastic resin particle dry blend material (C) according to claim
 5. 